trans-Tetra­aqua­bis­(isonicotinamide-κN 1)cobalt(II) bis­(3-hy­droxy­benzoate) tetra­hydrate

İIbrahim Göker Zaman; Nagihan Çaylak Delibaş; Hacali Necefoğlu; Tuncer Hökelek

doi:10.1107/S1600536812003911

. 2012 Feb 4;68(Pt 3):m249–m250. doi: 10.1107/S1600536812003911

trans-Tetraaquabis(isonicotinamide-κN ¹)cobalt(II) bis(3-hydroxybenzoate) tetrahydrate

İIbrahim Göker Zaman ^a, Nagihan Çaylak Delibaş ^b, Hacali Necefoğlu ^a, Tuncer Hökelek ^c,^*

PMCID: PMC3297218 PMID: 22412408

Abstract

The asymmetric unit of the title compound, [Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O, contains one-half of the complex cation with the Co^II ion located on an inversion center, a 3-hydroxybenzoate counter-anion and two uncoordinated water molecules. Four water O atoms in the equatorial plane around the Co^II ion [Co—O = 2.0593 (16) and 2.1118 (16) Å] form a slightly distorted square-planar arrangement, and the distorted octahedral geometry is completed by the two N atoms [Co—N = 2.1306 (18) Å] from two isonicotinamide ligands. In the anion, the carboxylate group is twisted from the attached benzene ring at 8.84 (17)°. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O—H⋯O and N—H⋯O hydrogen bonds, consolidates the crystal packing, which exhibits π–π interactions between the benzene and pyridine rings, with centroid–centroid distances of 3.458 (1) and 3.606 (1) Å, respectively.

Related literature

For related structures, see: Hökelek, Dal, Tercan, Özbek et al. (2009 ▶); Hökelek, Dal, Tercan, Aybirdi et al. (2009 ▶); Hökelek, Yılmaz, Tercan, Gürgen et al. (2009 ▶); Hökelek, Yılmaz, Tercan, Özbek et al. (2009 ▶); Hökelek, Yılmaz, Tercan, Sertçelik et al. (2009 ▶); Sertçelik et al. (2009a ▶,b ▶); Zaman et al. (2012 ▶).

Experimental

Crystal data

[Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M _r = 721.53
Monoclinic,
a = 6.7032 (2) Å
b = 17.0523 (4) Å
c = 13.5406 (3) Å
β = 100.194 (3)°
V = 1523.32 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 100 K
0.29 × 0.28 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.840, T _max = 0.916
14243 measured reflections
3779 independent reflections
3590 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.086
S = 1.23
3779 reflections
258 parameters
16 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003911/cv5239sup1.cif

e-68-0m249-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003911/cv5239Isup2.hkl

e-68-0m249-Isup2.hkl^{(181.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2ⁱ	0.86 (3)	2.18 (3)	3.031 (3)	170 (3)
N2—H22⋯O8ⁱⁱ	0.85 (4)	2.20 (4)	3.007 (3)	158 (3)
O3—H31⋯O7	0.91 (4)	1.81 (4)	2.711 (2)	170 (4)
O5—H51⋯O3ⁱⁱ	0.96 (3)	1.76 (3)	2.715 (2)	171 (3)
O5—H52⋯O2ⁱⁱⁱ	0.86 (3)	1.95 (4)	2.782 (2)	163 (4)
O6—H61⋯O4^iv	0.95 (3)	1.73 (3)	2.685 (2)	178 (4)
O6—H62⋯O2^v	0.82 (3)	1.89 (4)	2.683 (2)	161 (3)
O7—H71⋯O1ⁱ	0.98 (3)	1.76 (4)	2.740 (3)	179 (3)
O8—H81⋯O1	0.96 (4)	1.81 (4)	2.760 (3)	174 (3)
O8—H82⋯O7^vi	0.83 (5)	2.06 (4)	2.807 (3)	149 (5)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

The authors are indebted to Anadolu University and to the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer.

supplementary crystallographic information

Comment

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA) and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA) (Hökelek, Dal, Tercan, Özbek et al., 2009; Hökelek, Dal, Tercan, Aybirdi et al., 2009; Hökelek, Yılmaz, Tercan, Gürgen et al., 2009; Hökelek, Yılmaz, Tercan, Özbek et al., 2009; Hökelek, Yılmaz, Tercan, Sertçelik et al., 2009; Sertçelik et al., 2009a,b), the title compound was synthesized and its crystal structure is reported herein.

The title compound (I) is isostructural with the related Ni complex (Zaman et al., 2012). In (I) (Fig. 1), four O atoms (O5, O6, and the symmetry-related atoms, O5', O6') in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms (N1, N1') of the INA ligands at 2.1306 (18) Å from the Co atom in the axial positions (Fig. 1). The average Co—O bond length is 2.0856 (16) Å. The intramolecular O—H···O hydrogen bonds (Table 1) link the uncoordinated water molecules to the HB anion. The dihedral angle between the planar carboxylate group (O1/O2/C1) and the benzene ring A (C2—C7) is 8.84 (17)°, while that between rings A and B (N1/C8—C12) is 1.24 (7)°.

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. π–π Contacts between the benzene and pyridine rings, Cg1—Cg2 and Cg1—Cg2ⁱ, [symmetry code: (i) -1 + x, y, z, where Cg1 and Cg2 are centroids of the rings A (C2—C7) and B (N1/C8—C12), respectively] may further stabilize the structure, with centroid-centroid distances of 3.606 (1) and 3.458 (1) Å, respectively.

Experimental

The title compound was prepared by the reaction of CoSO₄.7H₂O (1.406 g, 5 mmol) in H₂O (100 ml) and INA (1.220 g, 10 mmol) in H₂O (50 ml) with sodium 3-hydroxybenzoate (1.601 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, giving orange single crystals.